JP6985219B2 - Manufacturing method of spherical silver powder - Google Patents
Manufacturing method of spherical silver powder Download PDFInfo
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- JP6985219B2 JP6985219B2 JP2018134378A JP2018134378A JP6985219B2 JP 6985219 B2 JP6985219 B2 JP 6985219B2 JP 2018134378 A JP2018134378 A JP 2018134378A JP 2018134378 A JP2018134378 A JP 2018134378A JP 6985219 B2 JP6985219 B2 JP 6985219B2
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 145
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 229910052709 silver Inorganic materials 0.000 claims description 88
- 239000004332 silver Substances 0.000 claims description 88
- 239000002245 particle Substances 0.000 claims description 74
- 239000003638 chemical reducing agent Substances 0.000 claims description 40
- 239000011164 primary particle Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 29
- PTYMQUSHTAONGW-UHFFFAOYSA-N carbonic acid;hydrazine Chemical compound NN.OC(O)=O PTYMQUSHTAONGW-UHFFFAOYSA-N 0.000 claims description 29
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- 238000001556 precipitation Methods 0.000 claims description 19
- -1 silver ions Chemical class 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 17
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- 230000001186 cumulative effect Effects 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 28
- 238000006722 reduction reaction Methods 0.000 description 27
- 239000002270 dispersing agent Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000005642 Oleic acid Substances 0.000 description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 150000002429 hydrazines Chemical class 0.000 description 3
- 238000007415 particle size distribution analysis Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 210000004180 plasmocyte Anatomy 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- VFWRGKJLLYDFBY-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag].[Ag] VFWRGKJLLYDFBY-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2201/00—Treatment under specific atmosphere
- B22F2201/01—Reducing atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/058—Particle size above 300 nm up to 1 micrometer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0466—Alloys based on noble metals
Description
本発明は、球状銀粉の製造方法に関する。本発明は、特に、積層コンデンサの内部電極、太陽電池、プラズマディスプレイパネル及びタッチパネル等の回路形成に使用される導電性ペーストに供される球状銀粉の製造方法に関する。 The present invention relates to a method for producing spherical silver powder. The present invention particularly relates to a method for producing spherical silver powder used for a conductive paste used for forming circuits such as internal electrodes of laminated capacitors, solar cells, plasma display panels and touch panels.
従来より、積層コンデンサの内部電極、回路基板の導体パターン、太陽電池やプラズマディスプレイパネル用基板の電極や回路などを形成する方法としては、例えば、銀粉をガラスフリットとともに有機ビヒクル中に加えて混練することによって製造される焼成型の導電性ペーストを基板上に所定のパターンに形成した後、５００℃以上の温度で加熱することによって、有機成分を除去し、銀粉同士を焼結させて導電膜を形成する方法が広く用いられている。 Conventionally, as a method for forming an internal electrode of a multilayer capacitor, a conductor pattern of a circuit board, an electrode of a substrate for a solar cell or a plasma display panel, a circuit, etc., for example, silver powder is added to an organic vehicle together with a glass frit and kneaded. After forming a firing-type conductive paste produced in this manner on a substrate in a predetermined pattern, the organic components are removed by heating at a temperature of 500 ° C. or higher, and the silver powders are sintered to form a conductive film. The method of forming is widely used.
このような用途に使用される導電性ペーストに対しては、電子部品の小型化へ対応するために、導体パターンの高密度化、ファインライン化などへの対応が要求される。そのため、使用される銀粉に対しては、粒径が適度に小さく粒度が揃っていること、有機ビヒクル中で分散していることが要求される。 For the conductive paste used for such applications, in order to cope with the miniaturization of electronic parts, it is required to cope with the high density of the conductor pattern, the fine line, and the like. Therefore, the silver powder used is required to have an appropriately small particle size and a uniform particle size, and to be dispersed in an organic vehicle.
こうした導電性ペースト用の銀粉を製造する方法として、例えば特許文献１において、銀イオンを含有する水性反応溶液に還元剤を混合することによって球状銀粉を還元析出させる湿式還元法が知られている。 As a method for producing silver powder for such a conductive paste, for example, in Patent Document 1, a wet reduction method for reducing and precipitating spherical silver powder by mixing a reducing agent with an aqueous reaction solution containing silver ions is known.
また、粒子径が揃っている球状銀粉を作成する製造法として、特許文献２には還元前に種粒子を混合してから還元析出させる方法が提案されており、特許文献３には銀イオンを含む水溶液と還元剤水溶液とを異なる流路より流し、接触混合して還元析出させる方法が提案されている。また、特許文献４には、銅粉末の製造方法として、複数種の還元剤を使用して還元析出させることが提案されている。 Further, as a manufacturing method for producing spherical silver powder having the same particle size, Patent Document 2 proposes a method of mixing seed particles before reduction and then reducing and precipitating, and Patent Document 3 contains silver ions. A method has been proposed in which an aqueous solution containing an aqueous solution and an aqueous reducing agent are flowed from different flow paths and contact-mixed for reduction precipitation. Further, Patent Document 4 proposes, as a method for producing a copper powder, reduction precipitation using a plurality of types of reducing agents.
上述したように、電子部品の小型化に伴い、微細な配線を描画できる導電性ペーストが求められている。ところで、導電性ペーストに使用する粉に粗粒が混在していると、該導電性ペーストを印刷する際のかすれの原因となり、その結果、配線の断線を招きかねない。また、粒子径がばらついている球状銀粉をペースト化すると、粘度特性にもばらつきが出てしまい、安定した印刷特性を出すことが難しくなる。 As described above, with the miniaturization of electronic components, there is a demand for a conductive paste capable of drawing fine wiring. By the way, if coarse particles are mixed in the powder used for the conductive paste, it causes faintness when printing the conductive paste, and as a result, the wiring may be broken. Further, when spherical silver powder having various particle sizes is made into a paste, the viscosity characteristics also vary, and it becomes difficult to obtain stable printing characteristics.
また、太陽電池用途での電極作製においては、焼成時間を数１０秒と非常に短時間で焼結させるのが通常である。焼結させる際に、導電性ペーストに粗粒が多く含まれると、導電性ペーストは焼結不足を引き起こしてしまい、一方、微粒が多く含まれると、導電性ペーストの焼結が促進されて過焼結を引き起こしてしまう。したがって、短時間で適切な焼結状態を達成するためにも、球状銀粉の粒子径を適切に制御できる技術が非常に重要である。 Further, in the production of electrodes for solar cell applications, it is usual to sinter in a very short firing time of several tens of seconds. When sintering, if the conductive paste contains a large amount of coarse particles, the conductive paste causes insufficient sintering, while if a large amount of fine particles are contained, the sintering of the conductive paste is promoted and excessive. It causes sintering. Therefore, in order to achieve an appropriate sintering state in a short time, a technique capable of appropriately controlling the particle size of the spherical silver powder is very important.
前記したような理由から、粒子径のばらつきが小さい球状銀粉が求められている。 For the reasons described above, there is a demand for spherical silver powder having a small variation in particle size.
さて、前掲した特許文献２〜４に開示される粒子径を揃えた金属粉の製造法では、次のような問題点がある。 By the way, the above-mentioned method for producing a metal powder having a uniform particle size disclosed in Patent Documents 2 to 4 has the following problems.
まず、特許文献２のように、種粒子を使用した製造方法では、種粒子を作製する工程が追加されるために、製造工程が複雑化する。また、種粒子作製のために使用する分散剤が、目的粒子の作製時に副作用する虞もある。 First, in the manufacturing method using seed particles as in Patent Document 2, the manufacturing process is complicated because a step for producing seed particles is added. In addition, the dispersant used for producing seed particles may have side effects when producing target particles.
また、特許文献３のように、銀イオンを含む水溶液と還元剤水溶液を異なる流路より流し、接触混合して還元析出させる方法では、接触配管内に銀鏡反応が起こった場合に管内が閉塞してしまう虞もある。 Further, in the method as in Patent Document 3, in which an aqueous solution containing silver ions and a reducing agent aqueous solution are flowed from different flow paths and contact-mixed for reduction precipitation, the inside of the contact pipe is closed when a silver mirror reaction occurs. There is also a risk that it will end up.
さらに、特許文献４のように、複数種の還元剤を用いる方法では、還元剤を単独で用いたときよりも排水処理が複雑になると考えられ、結果として製造コストが増加してしまう。 Further, in the method using a plurality of kinds of reducing agents as in Patent Document 4, it is considered that the wastewater treatment becomes more complicated than when the reducing agent is used alone, and as a result, the manufacturing cost increases.
そこで本発明は、上記のような諸問題を解決し、従来よりも一次粒子径のばらつきが小さい球状銀粉を簡便に製造することのできる球状銀粉の製造方法の提供を目的とする。 Therefore, an object of the present invention is to provide a method for producing spherical silver powder, which solves the above-mentioned problems and can easily produce spherical silver powder having a smaller variation in primary particle size than the conventional one.
前記諸課題を解決するため本発明者らが鋭意研究を重ねた結果、銀イオンを含有する水性反応系に還元剤として炭酸ヒドラジンを混合して銀粒子を還元析出させることによって、一次粒子径の揃った球状銀粉を製造できることを知見した。炭酸ヒドラジンを還元剤として使用する場合の方がヒドラジン水溶液（ヒドラジン水和物）を使用した場合と比較して一次粒子径が揃う理由は定かではないものの、炭酸ヒドラジン分子（ＮＨ2ＮＨ2）2・ＣＯ2に付いている炭酸が脱離してから還元が始まるため、還元剤の投入から還元開始までの間に銀イオンを含有する水性反応系中に反応前のヒドラジン（Ｎ2Ｈ4）が十分に分散するだけの猶予時間が得られ、銀イオンを含有する水性反応系と、炭酸ヒドラジンとの混合溶液内での均一な核生成と成長が達成されるためと予想される。
本発明は上記知見に基づき完成したものであり、具体的には以下のとおりである。
As a result of diligent research by the present inventors in order to solve the above-mentioned problems, hydrazine carbonate is mixed as a reducing agent in an aqueous reaction system containing silver ions to reduce and precipitate silver particles, thereby increasing the primary particle size. It was found that a complete spherical silver powder can be produced. Although it is not clear why the primary particle size is uniform when hydrazine carbonate is used as a reducing agent compared to when an aqueous hydrazine solution (hydrazine hydrate) is used, hydrazine carbonate molecule (NH 2 NH 2 ) 2 -Since the reduction starts after the carbon dioxide attached to CO 2 is desorbed, hydrazine (N 2 H 4 ) before the reaction is contained in the aqueous reaction system containing silver ions between the addition of the reducing agent and the start of the reduction. It is expected that a grace period for sufficient dispersion will be obtained, and uniform nucleation and growth will be achieved in the mixed solution of the aqueous reaction system containing silver ions and hydrazine carbonate.
The present invention has been completed based on the above findings, and the specifics are as follows.
（１）銀イオンを含有する水性反応系に、炭酸ヒドラジンからなる還元剤を混合して、銀粒子を還元析出させる還元析出工程を含む、球状銀粉の製造方法。 (1) A method for producing spherical silver powder, which comprises a reduction precipitation step of mixing a reducing agent composed of hydrazine carbonate with an aqueous reaction system containing silver ions to reduce and precipitate silver particles.
（２）前記還元析出工程において混合する前記炭酸ヒドラジンの量が、銀に対して１〜６モル当量である、前記（１）に記載の球状銀粉の製造方法。 (2) The method for producing spherical silver powder according to (1) above, wherein the amount of the hydrazine carbonate to be mixed in the reduction precipitation step is 1 to 6 molar equivalents with respect to silver.
（３）前記銀イオンを含有する前記水性反応系が銀アンミン錯体であり、
該銀アンミン錯体は、硝酸銀、銀錯体及び銀中間体の少なくともいずれかを含有する水溶液にアンモニア水又はアンモニウム塩を添加することにより調液される、前記（１）または（２）に記載の球状銀粉の製造方法。
(3) The aqueous reaction system containing the silver ion is a silver ammine complex.
The spherical shape according to (1) or (2) above, wherein the silver ammine complex is prepared by adding aqueous ammonia or an ammonium salt to an aqueous solution containing at least one of silver nitrate, a silver complex and a silver intermediate. How to make silver powder.
（４）前記還元析出工程において前記還元剤を混合するときの前記銀イオンを含有する前記水性反応系の温度が１０〜５０℃である、前記（１）〜（３）のいずれかに記載の球状銀粉の製造方法。 (4) The above-mentioned (1) to (3), wherein the temperature of the aqueous reaction system containing the silver ion when the reducing agent is mixed in the reduction precipitation step is 10 to 50 ° C. A method for producing spherical silver powder.
（５）前記球状銀粉のＳＥＭ一次粒子径の累積５０％粒子径Ｄ５０が０．１〜１．５μｍであり、かつ、粒度分布における変動係数が０．２以下である、前記（１）〜（４）のいずれかに記載の球状銀粉の製造方法。 (5) The cumulative 50% particle diameter D50 of the SEM primary particle diameter of the spherical silver powder is 0.1 to 1.5 μm, and the coefficient of variation in the particle size distribution is 0.2 or less. The method for producing spherical silver powder according to any one of 4).
本発明によれば、従来よりも一次粒子径のばらつきが小さい球状銀粉を簡便に製造することのできる球状銀粉の製造方法を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing spherical silver powder, which can easily produce spherical silver powder having a smaller variation in primary particle diameter than the conventional one.
本明細書中において、「ＳＥＭ一次粒子径」とは、走査電子顕微鏡（ＳＥＭ）から求められる一次粒子径をいう。このＳＥＭ一次粒子径の累積５０％粒子径Ｄ５０は、銀粒子を走査電子顕微鏡（ＳＥＭ）により倍率１万倍で観察し、無作為に選んだ視野内で観察される銀粒子（一次粒子）の中で他の粒子との重なりや結合が無く輪郭のはっきりしている銀粒子から無作為に抽出した１００個について、画像解析式粒度分布測定ソフトウェア（株式会社マウンテック製のＭａｃ−Ｖｉｅｗ）を用いて、各々の銀粒子の円相当径（Ｈｅｙｗｏｏｄ径）に換算することでそれぞれの銀粒子の粒径を求め、個数基準の粒度分布の累積値が５０％を示す５０％粒径として求めたものである。 In the present specification, the "SEM primary particle size" means the primary particle size obtained from a scanning electron microscope (SEM). The cumulative 50% particle size D50 of the SEM primary particle size is the same as that of silver particles (primary particles) observed in a randomly selected visual field by observing silver particles with a scanning electron microscope (SEM) at a magnification of 10,000 times. Using image analysis type particle size distribution measurement software (Mac-View manufactured by Mountech Co., Ltd.), 100 particles randomly selected from silver particles with clear outlines that do not overlap or bond with other particles are used. , The particle size of each silver particle was obtained by converting it to the equivalent circle diameter (Heywood diameter) of each silver particle, and the cumulative value of the particle size distribution based on the number was obtained as 50% particle size indicating 50%. be.
本発明による球状銀粉の製造方法は、銀粒子を還元析出させる還元析出工程を含む。さらに必要に応じて、適宜選択したその他の工程を含む。その他の工程として、銀イオン分散液の調液工程、分散剤の吸着工程、回収洗浄工程、乾燥工程、及び乾式処理工程を例示することができる。すなわち、本発明による球状銀粉の製造方法は、銀粒子を還元析出させる還元析出工程のほか、任意に、銀イオン分散液の調液工程、分散剤の吸着工程、回収洗浄工程、乾燥工程、及び乾式処理工程を含むことができる。 The method for producing spherical silver powder according to the present invention includes a reduction precipitation step of reducing and precipitating silver particles. Further, if necessary, other steps selected as appropriate are included. As other steps, a liquid preparation step of the silver ion dispersion liquid, a adsorption step of the dispersant, a recovery cleaning step, a drying step, and a dry treatment step can be exemplified. That is, in the method for producing spherical silver powder according to the present invention, in addition to the reduction precipitation step of reducing and precipitating silver particles, a liquid preparation step of a silver ion dispersion liquid, a dispersant adsorption step, a recovery cleaning step, a drying step, and an optional step. A dry treatment step can be included.
以下、本発明の実施の形態について、具体的態様を含めて次の順序で説明を行う。
１−Ａ）銀イオン分散液の調液工程
１−Ｂ）還元析出工程
１−Ｃ）分散剤の吸着工程
１−Ｄ）回収洗浄工程
１−Ｅ）乾燥工程
１−Ｆ）乾式処理工程
Hereinafter, embodiments of the present invention will be described in the following order, including specific embodiments.
1-A) Preparation step of silver ion dispersion 1-B) Reduction precipitation step 1-C) Dispersant adsorption step 1-D) Recovery cleaning step 1-E) Drying step 1-F) Dry treatment step
１−Ａ）銀イオン分散液の調液工程
本工程は、球状銀粉の基となる銀粒子を生成するための銀イオン分散液を調液する工程であり、本工程により得られた銀イオン分散液を銀イオンを含有する水性反応系として用いることができる。
銀イオンを含有する水性反応系としては、硝酸銀、銀錯体及び銀中間体の少なくともいずれかを含有する水溶液又はスラリーを使用することができる。銀粒子の成長の核となる種粒子を用いてもよいが、反応系が複雑になるため、種粒子は用いない方がより好ましい。
銀錯体を含有する水溶液は、硝酸銀水溶液又は酸化銀懸濁液にアンモニア水又はアンモニウム塩を添加することにより生成することができる。これらの中でも、球状銀粉が適当な粒径と球形状を有するようにするためには、硝酸銀水溶液にアンモニア水を添加して得られる銀アンミン錯体水溶液を使用することが好ましい。
銀アンミン錯体中におけるアンモニアの配位数は２であるため、銀１モルに対してアンモニア２モルが反応する。銀に対してアンモニア１モル当量以上を添加することが好ましく、２モル当量以上を添加することがより好ましい。このとき、アンモニア１モル当量とは銀１モルに対してアンモニア２モル分に相当する。また、錯体をある程度反応しやすくするべく、アンモニアの添加量は銀に対してアンモニア８モル当量以下とすることができ、６モル当量以下とすることが好ましい。また、銀イオンを含有する水性反応系にｐＨ調整剤を添加してもよい。ｐＨ調整剤としては、一般的な酸や塩基を使用することができ、例えば、硝酸、水酸化ナトリウムなどが挙げられる。
なお、上記の銀中間体とは、目的となる物質をつくる反応途中で作られる物質のことを指し、銀中間体としては例えば酸化銀（Ａｇ2Ｏ）や炭酸銀（Ａｇ2ＣＯ3）などが挙げられる。これらはアンミン錯体を作る過程でアンモニアを加えることによって溶解し、大部分の銀イオンは銀アンミン錯体として存在するようになる。
1-A) Preparation step of silver ion dispersion This step is a step of preparing a silver ion dispersion for producing silver particles which are the basis of spherical silver powder, and the silver ion dispersion obtained by this step. The liquid can be used as an aqueous reaction system containing silver ions.
As the aqueous reaction system containing silver ions, an aqueous solution or slurry containing at least one of silver nitrate, a silver complex and a silver intermediate can be used. Although seed particles that are the core of the growth of silver particles may be used, it is more preferable not to use seed particles because the reaction system becomes complicated.
The aqueous solution containing the silver complex can be produced by adding aqueous ammonia or an ammonium salt to the aqueous silver nitrate solution or the silver oxide suspension. Among these, in order for the spherical silver powder to have an appropriate particle size and spherical shape, it is preferable to use a silver ammine complex aqueous solution obtained by adding ammonia water to the silver nitrate aqueous solution.
Since the coordination number of ammonia in the silver ammine complex is 2, 2 mol of ammonia reacts with 1 mol of silver. It is preferable to add 1 mol equivalent or more of ammonia to silver, and it is more preferable to add 2 mol equivalent or more. At this time, 1 mol equivalent of ammonia corresponds to 2 mol of ammonia with respect to 1 mol of silver. Further, in order to facilitate the reaction of the complex to some extent, the amount of ammonia added can be 8 molar equivalents or less with respect to silver, preferably 6 molar equivalents or less. Further, a pH adjuster may be added to the aqueous reaction system containing silver ions. As the pH adjuster, a general acid or base can be used, and examples thereof include nitric acid and sodium hydroxide.
The above-mentioned silver intermediate refers to a substance produced during the reaction to produce a target substance, and examples of the silver intermediate include silver oxide (Ag 2 O) and silver carbonate (Ag 2 CO 3 ). Can be mentioned. These are dissolved by adding ammonia in the process of forming the ammine complex, and most of the silver ions come to exist as the silver ammine complex.
１−Ｂ）還元析出工程
本工程においては、還元剤により銀イオンを含有する水性反応系（銀イオン分散液）から銀を還元析出する。
還元剤としては炭酸ヒドラジンを用いる。なお、ここで言う「炭酸ヒドラジン」には、炭酸ヒドラジンを希釈した炭酸ヒドラジン水溶液も含まれる。本発明においては、炭酸ヒドラジン以外の還元剤を用いないことが好ましいため、「炭酸ヒドラジン」はアルデヒド基を有する化合物とは異なる種類の還元剤を含まないことが好ましい。また、排水処理を簡便化するため、本工程のみにおいて還元剤を使用することが好ましく、この場合、１−Ａ）銀イオン分散液の調液工程の後の１−Ｂ）還元工程のみにおいて還元剤を使用することとなる。使用する炭酸ヒドラジンとしては、例えば、大塚化学株式会社製や日本ファインケム株式会社製より市販のものを用いることができる。他にも、通常のヒドラジン水溶液に炭酸ガスを吹き込んで調製したものを使用してもよい（過半が炭酸ヒドラジンであれば炭酸塩となっていないヒドラジンが一部含まれていてもよい）。
1-B) Reduction and precipitation step In this step, silver is reduced and precipitated from an aqueous reaction system (silver ion dispersion) containing silver ions by a reducing agent.
Hydrazine carbonate is used as the reducing agent. The term "hydrazine carbonate" as used herein also includes an aqueous solution of hydrazine carbonate obtained by diluting hydrazine carbonate. In the present invention, since it is preferable not to use a reducing agent other than hydrazine carbonate, it is preferable that "hydrazine carbonate" does not contain a reducing agent of a type different from that of the compound having an aldehyde group. Further, in order to simplify the wastewater treatment, it is preferable to use a reducing agent only in this step. In this case, 1-A) reduction in 1-B) reduction step after the preparation step of the silver ion dispersion. The agent will be used. As the hydrazine carbonate to be used, for example, those commercially available from Otsuka Chemical Co., Ltd. and Japan Finechem Co., Ltd. can be used. Alternatively, a normal hydrazine aqueous solution prepared by blowing carbon dioxide gas may be used (if the majority is carbonate hydrazine, some hydrazine that is not carbonate may be contained).
還元剤の量は、銀の反応収率を上げるために、銀に対して１モル当量以上とすることができ、１．１モル当量以上としてもよい。一方、還元剤の過剰な使用は原料コスト及び排水処理のコストを増加させてしまう可能性がある。そのため、混合する還元剤の量は、銀に対して６モル当量以下とするが好ましく、５モル当量以下とすることがより好ましい。また、銀イオンを含有する水性反応系に炭酸ヒドラジンを混合する際の炭酸ヒドラジンの濃度は、１〜７０質量％の範囲が好ましい。なお、炭酸ヒドラジン分子式は（Ｎ2Ｈ4）2・ＣＯ2のため１分子で通常のヒドラジン２つ分の働きがあり、ヒドラジンは還元時に電子を４つ放出するため、銀１モルに対して炭酸ヒドラジンは１／８モルで反応する。つまり、銀に対して炭酸ヒドラジン１モル当量とは銀１モルに対して炭酸ヒドラジン１／８モル分に相当する。 The amount of the reducing agent may be 1 molar equivalent or more, or 1.1 molar equivalent or more, with respect to silver in order to increase the reaction yield of silver. On the other hand, excessive use of reducing agents may increase raw material costs and wastewater treatment costs. Therefore, the amount of the reducing agent to be mixed is preferably 6 molar equivalents or less, more preferably 5 molar equivalents or less with respect to silver. The concentration of hydrazine carbonate when mixed with the aqueous reaction system containing silver ions is preferably in the range of 1 to 70% by mass. Since the molecular formula of hydrazine carbonate is (N 2 H 4 ) 2 · CO 2 , one molecule has the function of two normal hydrazines, and hydrazine emits four electrons during reduction, so for 1 mol of silver. Hydrazine carbonate reacts at 1/8 mol. That is, 1 mol equivalent of hydrazine carbonate with respect to silver corresponds to 1/8 mol of hydrazine carbonate with respect to 1 mol of silver.
また、本工程において、還元剤を混合するときの前記銀イオンを含有する前記水性反応系の温度は、１０〜５０℃であることが好ましく、２０〜４０℃であることがより好ましい。水性反応系の温度の好適範囲は２０〜４０℃である。温度が高いと炭酸脱離が早くなり、反応前のヒドラジン（Ｎ2Ｈ4）が十分に拡散する時間を設けられなくなる可能性があり、温度が低いと炭酸脱離後のヒドラジンの反応性が悪くなり還元析出が十分に行われなくなる可能性があるからである。 Further, in this step, the temperature of the aqueous reaction system containing the silver ion when the reducing agent is mixed is preferably 10 to 50 ° C, more preferably 20 to 40 ° C. The preferred range of temperature for the aqueous reaction system is 20-40 ° C. If the temperature is high, the hydrazine desorption will be accelerated, and it may not be possible to provide sufficient time for the hydrazine (N 2 H 4 ) before the reaction to diffuse sufficiently. If the temperature is low, the reactivity of the hydrazine after the carbon dioxide desorption may be reduced. This is because there is a possibility that the reduction precipitation will not be sufficiently performed due to deterioration.
また、本工程は連続混合及びバッチ式混合のいずれで行ってもよい。ただし、バッチ式の混合処理の場合、還元剤の全量を、銀イオンを含有する水性反応系（すなわち銀イオン分散液）と混合するまでに要する時間をできるだけ短くすることが好ましい。バッチ式の混合処理では、容積（バッチ処理での銀粉の収量）が増えるほど、短時間で還元剤を混合することは難しくなる。そして、混合中の銀イオン分散液を十分に撹拌していても、還元剤の導入領域に近い領域と遠い領域とでの銀イオン分散液内での還元剤濃度の差が生じているうちに還元析出反応が起きれば、得られる球状銀粉の一次粒子径のばらつきが増える要因の一つともなり得る。
そこで、本発明は従来技術と異なり、還元剤として炭酸ヒドラジンを用いる。炭酸ヒドラジンを使用するために、還元剤が銀イオンを含有する水性反応系と接触してから還元反応が開始するまでの時間（猶予時間）が生ずる。そのため、還元剤が撹拌されて還元剤濃度差を低減するための時間をより長く確保することができる。バッチ処理での銀粉の収量を同容積で比較すると、従来よりも一次粒子径のばらつきが小さい球状銀粉を簡便に製造することができる点で本発明は有利である。一方、容積を変えて比較すると、量産性（すなわち、多くの銀粉を同時に均一に製造する能力）を向上できる点でも本発明は有利である。
Further, this step may be performed by either continuous mixing or batch mixing. However, in the case of a batch-type mixing treatment, it is preferable to shorten the time required for mixing the entire amount of the reducing agent with the aqueous reaction system containing silver ions (that is, the silver ion dispersion) as much as possible. In the batch-type mixing process, it becomes difficult to mix the reducing agent in a short time as the volume (yield of silver powder in the batch process) increases. Then, even if the silver ion dispersion liquid being mixed is sufficiently stirred, the difference in the reducing agent concentration in the silver ion dispersion liquid occurs between the region near the region where the reducing agent is introduced and the region far from the reducing agent introduction region. If the reduction precipitation reaction occurs, it can be one of the factors that increase the variation in the primary particle size of the obtained spherical silver powder.
Therefore, unlike the prior art, the present invention uses hydrazine carbonate as a reducing agent. Due to the use of hydrazine carbonate, there is a time (grace time) from when the reducing agent comes into contact with the aqueous reaction system containing silver ions until the reduction reaction starts. Therefore, it is possible to secure a longer time for the reducing agent to be agitated to reduce the difference in reducing agent concentration. Comparing the yields of silver powder in batch processing at the same volume, the present invention is advantageous in that spherical silver powder having a smaller variation in primary particle size than the conventional one can be easily produced. On the other hand, the present invention is also advantageous in that mass productivity (that is, the ability to uniformly produce a large amount of silver powder at the same time) can be improved when compared by changing the volume.
なお、炭酸ヒドラジン以外のヒドラジン誘導体として、例えば、塩酸ヒドラジンや硫酸ヒドラジンを還元剤として用いることは考えられるものの、これら分子内の塩素成分または硫黄成分が銀と反応して塩化銀や硫化銀を生成してしまう。さらに、焼結後も塩素成分または硫黄成分が粉体内に残存することにより、腐食を促進してしまう。また、その他のヒドラジン化合物では、ヒドラジンを部分的に置換反応させていることから、１分子あたりの電子の放出数が少なくなり、必要な還元剤混合量が増加してしまう可能性がある。さらに、ヒドラジンを置換反応させるためのコスト増加により球状銀粉の製造コストも増加してしまい、且つ、排水処理も通常のヒドラジンに比べてコストがかかることが予想される。上記のような理由から、本発明における還元剤としては炭酸ヒドラジンが適している。 Although it is conceivable to use, for example, hydrazine hydrochloride or hydrazine sulfate as a reducing agent as a hydrazine derivative other than hydrazine carbonate, the chlorine component or sulfur component in these molecules reacts with silver to generate silver chloride or silver sulfide. Resulting in. Further, even after sintering, the chlorine component or the sulfur component remains in the powder, which promotes corrosion. Further, in other hydrazine compounds, since the hydrazine is partially substituted, the number of electrons emitted per molecule may decrease, and the required mixing amount of the reducing agent may increase. Further, it is expected that the production cost of spherical silver powder will increase due to the increase in the cost for the substitution reaction of hydrazine, and the wastewater treatment will be more costly than that of ordinary hydrazine. For the above reasons, hydrazine carbonate is suitable as the reducing agent in the present invention.
１−Ｃ）分散剤の吸着工程
本工程においては、各銀粒子の表面に分散剤を吸着させる。
球状銀粉の還元析出前および還元析出後に分散剤を液中に添加することで銀粉表面へ分散剤を吸着させることができる。分散剤の添加は還元前だけでもよいし、還元後だけでもよいし、還元の前後で分散剤を添加してもよい。
吸着工程における有機物などの分散剤の添加量は、銀粉質量に対して合計０．０５質量％以上３．０質量％以下が好ましく、０．１質量％以上１．０質量％以下がより好ましい。
分散剤としては、特に制限はなく目的に応じて適宜選択することができる。例えば脂肪酸およびその塩、界面活性剤、有機金属化合物、キレート剤、高分子分散剤などを挙げることができる。分散剤は単独で使用してもよいし、２種類以上を併用してもよい。
1-C) Dispersant adsorption step In this step, the dispersant is adsorbed on the surface of each silver particle.
By adding the dispersant to the liquid before and after the reduction precipitation of the spherical silver powder, the dispersant can be adsorbed on the surface of the silver powder. The dispersant may be added only before the reduction, after the reduction, or before and after the reduction.
The total amount of the dispersant such as organic substances added in the adsorption step is preferably 0.05% by mass or more and 3.0% by mass or less, and more preferably 0.1% by mass or more and 1.0% by mass or less with respect to the mass of the silver powder.
The dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include fatty acids and salts thereof, surfactants, organometallic compounds, chelating agents, polymer dispersants and the like. The dispersant may be used alone or in combination of two or more.
１−Ｄ）回収洗浄工程
上記の各工程を経た上で、本工程において、得られた銀粒子を回収し、洗浄する。回収と洗浄とは互いに別工程としても、複数回繰り返しても、同時進行としてもよい。
上記の還元工程を経て得られた銀粉には、大抵の場合、不純物が含有しているため洗浄することが好ましい。ここで洗浄に用いられる洗浄溶媒としては、純水が好適である。
回収及び洗浄の方式としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、デカンテーションやろ過などが挙げられる。洗浄の終点は、洗浄後の水の電気伝導度を用いて判断することができ、電気伝導度が０．５ｍＳ／ｍ以下になるまで洗浄を実施するのが好適である。
1-D) Recovery and cleaning step After going through each of the above steps, the silver particles obtained in this step are recovered and washed. Recovery and cleaning may be separate processes, repeated multiple times, or simultaneously performed.
In most cases, the silver powder obtained through the above reduction step contains impurities, so that it is preferable to wash the silver powder. Pure water is suitable as the cleaning solvent used for cleaning here.
The method of collection and cleaning is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include decantation and filtration. The end point of the washing can be determined by using the electric conductivity of the water after the washing, and it is preferable to carry out the washing until the electric conductivity becomes 0.5 mS / m or less.
１−Ｅ）乾燥工程
本工程においては、回収洗浄工程後の銀粒子の集合体を乾燥する。
上記の回収洗浄工程後の銀粒子の集合体は多くの水分を含有したケーキまたはスラリーとなっている。そのため、銀粒子を最終的に銀粉として使用可能とすべく、当該ケーキまたはスラリーから水分を除去する必要がある。
水分除去の方法としては、乾燥した風を送る、減圧する、乾きやすい溶媒につける、圧縮空気で吹き飛ばす、遠心力で振り切るなどがあるが、減圧下で温めるのが簡易的である。乾燥温度は、銀粉同士の焼結を抑制可能な１００℃以下とするのが好適である。
1-E) Drying step In this step, the aggregate of silver particles after the recovery and washing step is dried.
The aggregate of silver particles after the above recovery and washing step is a cake or slurry containing a large amount of water. Therefore, it is necessary to remove water from the cake or slurry so that the silver particles can be finally used as silver powder.
Moisture removal methods include sending dry air, reducing the pressure, soaking in a solvent that dries easily, blowing off with compressed air, and shaking off with centrifugal force, but warming under reduced pressure is simple. The drying temperature is preferably 100 ° C. or lower, which can suppress the sintering of silver powders.
１−Ｆ）乾式処理工程
上記乾燥工程を経て得られた銀粉に対し、乾式解砕処理や分級処理などの乾式処理工程を施してもよい。また、銀粉を機械的に流動化させることができる装置に銀粉を投入して、銀粉の銀粒子同士を機械的に衝突させることによって、銀粒子の表面の角張った部分を滑らかにする表面平滑化処理を行ってもよい。加えて、解砕や平滑化処理の後に分級処理を行ってもよい。なお、乾燥、粉砕及び分級を行うことができる一体型の装置を用いて乾燥、粉砕及び分級を行ってもよい。上記の工程を経て得られる球状銀粉のＳＥＭ一次粒子径の累積５０％粒子径（Ｄ５０）を０．１〜１．５μｍとすることができ、かつ、粒度分布における変動係数を０．２以下とすることができる。さらには、Ｄ５０を０．２〜１．０μｍとすることができる。
1-F) Dry-type treatment step The silver powder obtained through the above-mentioned drying step may be subjected to a dry-type treatment step such as a dry-type crushing treatment or a classification treatment. In addition, the silver powder is put into a device capable of mechanically fluidizing the silver powder, and the silver particles of the silver powder are mechanically collided with each other to smooth the angular portion of the surface of the silver particles. Processing may be performed. In addition, classification treatment may be performed after crushing or smoothing treatment. In addition, drying, crushing, and classification may be performed using an integrated device capable of performing drying, crushing, and classification. The cumulative 50% particle size (D50) of the SEM primary particle size of the spherical silver powder obtained through the above steps can be 0.1 to 1.5 μm, and the coefficient of variation in the particle size distribution is 0.2 or less. can do. Furthermore, D50 can be set to 0.2 to 1.0 μm.
上述した本発明による球状銀粉の製造方法では、従来の製造方法と比べても、高価な試薬や複雑な工程を用いる必要がなく、排水処理についても、従来のヒドラジン水溶液を用いた場合と同様に行うことができる。そのため、生産コストを大きく増加させる必要もない。そして、この製造方法に従い、従来よりも一次粒子径のばらつきが小さい球状銀粉を簡便に製造することができる。そして、この製造方法により得られる球状銀粉は、一次粒子径のばらつきが小さい。 The above-mentioned method for producing spherical silver powder according to the present invention does not require the use of expensive reagents or complicated steps as compared with the conventional production method, and the wastewater treatment is the same as in the case of using the conventional hydrazine aqueous solution. It can be carried out. Therefore, it is not necessary to significantly increase the production cost. Then, according to this production method, it is possible to easily produce spherical silver powder having a smaller variation in the primary particle size than the conventional one. The spherical silver powder obtained by this production method has a small variation in the primary particle size.
以下、本発明による球状銀粉の実施例について詳細に説明するが、本発明は以下の実施例に何ら限定されるものではない。 Hereinafter, examples of the spherical silver powder according to the present invention will be described in detail, but the present invention is not limited to the following examples.
（実施例１）
銀イオンとして０．１２ｍｏｌ／Ｌ含有する硝酸銀水溶液を３．２Ｌ準備し、前記硝酸銀水溶液に濃度２８質量％のアンモニア水溶液を１３７．７ｇ（銀に対して２．７モル当量相当）加えて銀アンミン錯体水溶液を得た。また、７０質量％炭酸ヒドラジン水溶液１４．６ｇ（大塚化学株式会社製、銀量に対して１．８モル当量相当）を純水１３１．４ｇで希釈して還元剤を得た。この銀アンミン錯体水溶液の液温を３０．０℃に維持し、十分に撹拌している銀アンミン錯体溶液に混合して、銀粉を含むスラリーを得た。混合の開始から１．０秒後に溶液の変色が開始し、還元析出反応が起きたことが分かった。
更に得られた銀粉を含むスラリーに対して、分散剤としてエタノールにオレイン酸を５．０質量％になるように溶かした溶液を３．６ｇ加え、十分に撹拌した後、熟成させた。オレイン酸の添加量は、銀粉の質量に対して０．４質量％である。前記熟成されたスラリーを濾過、水洗した後、真空乾燥機を用いて７３℃で１０時間乾燥させた。その後、得られた乾燥粉を解砕機（協立理工株式会社製、ＳＫ−Ｍ１０型）に投入し、３０秒間の解砕を２回繰り返した。このようにして実施例１の球状銀粉を得た。
(Example 1)
Prepare 3.2 L of a silver nitrate aqueous solution containing 0.12 mol / L as silver ions, and add 137.7 g (equivalent to 2.7 mol equivalents to silver) of an ammonia aqueous solution having a concentration of 28% by mass to the silver nitrate aqueous solution to make silver ammine. An aqueous complex solution was obtained. Further, 14.6 g of a 70 mass% hydrazine carbonate aqueous solution (manufactured by Otsuka Chemical Co., Ltd., equivalent to 1.8 molar equivalents with respect to the amount of silver) was diluted with 131.4 g of pure water to obtain a reducing agent. The liquid temperature of this silver ammine complex aqueous solution was maintained at 30.0 ° C., and the mixture was mixed with a sufficiently stirred silver ammine complex solution to obtain a slurry containing silver powder. It was found that the discoloration of the solution started 1.0 second after the start of mixing, and the reduction precipitation reaction occurred.
Further, to the obtained slurry containing silver powder, 3.6 g of a solution prepared by dissolving oleic acid in ethanol in an amount of 5.0% by mass as a dispersant was added, and the mixture was sufficiently stirred and then aged. The amount of oleic acid added is 0.4% by mass with respect to the mass of silver powder. The aged slurry was filtered, washed with water, and then dried at 73 ° C. for 10 hours using a vacuum dryer. Then, the obtained dry powder was put into a crusher (SK-M10 type manufactured by Kyoritsu Riko Co., Ltd.), and crushing for 30 seconds was repeated twice. In this way, the spherical silver powder of Example 1 was obtained.
得られた実施例１の球状銀粉を、走査型電子顕微鏡（ＳＥＭ）を用いて倍率１００００倍で撮影した。撮影した画像を図１に示す。 The obtained spherical silver powder of Example 1 was photographed with a scanning electron microscope (SEM) at a magnification of 10000 times. The captured image is shown in FIG.
また、撮影したＳＥＭ画像（図１）について、画像解析ソフト（株式会社マウンテック製Ｍａｃ−Ｖｉｅｗ）を用いて、得られた球状銀粉の銀粒子の一次粒子径の粒度分布を解析した。
当該解析ソフトは、任意の粒子の輪郭をなぞると粒子面積が算出され、それを円相当径（Ｈｅｙｗｏｏｄ径）に換算することで粒径を算出している。これを画像内の粒子１００個に対して行い、測定結果を粒度分布としてグラフ化した。この粒度分布を図２に示す。測定粒子は、ＳＥＭ画像において他の粒子との重なりや結合が無く輪郭のはっきりしているものを任意に選択した。粒度分布は分布幅が狭いと標準偏差が小さくなり、粒径のばらつきが小さく、揃った銀粉であることを意味する。また、粒子径の異なる場合において、粒子径ばらつきの相対的な評価を行うために変動係数を求めた。変動係数はＳＥＭ一次粒子径から求めた粒度分布の標準偏差をＤ５０で除したもので、ＳＥＭ一次粒子径のばらつき大きさの指標となる。
解析の結果、球状銀粉の累積５０％粒子径（Ｄ５０）は０．３４μｍ、粒度分布の標準偏差は０．０６３μｍであり、変動係数は０．１８５であった。
Further, with respect to the photographed SEM image (FIG. 1), the particle size distribution of the primary particle size of the silver particles of the obtained spherical silver powder was analyzed using image analysis software (Mac-View manufactured by Mountech Co., Ltd.).
In the analysis software, the particle area is calculated by tracing the contour of an arbitrary particle, and the particle size is calculated by converting it into a circle-equivalent diameter (Heywood diameter). This was done for 100 particles in the image, and the measurement results were graphed as a particle size distribution. This particle size distribution is shown in FIG. As the measurement particles, those having a clear outline without overlapping or bonding with other particles in the SEM image were arbitrarily selected. The particle size distribution means that when the distribution width is narrow, the standard deviation becomes small, the variation in particle size is small, and the silver powder is uniform. In addition, when the particle size is different, the coefficient of variation was obtained in order to evaluate the relative particle size variation. The coefficient of variation is obtained by dividing the standard deviation of the particle size distribution obtained from the SEM primary particle size by D50, and is an index of the variation size of the SEM primary particle size.
As a result of the analysis, the cumulative 50% particle size (D50) of the spherical silver powder was 0.34 μm, the standard deviation of the particle size distribution was 0.063 μm, and the coefficient of variation was 0.185.
（実施例２）
銀イオンとして０．１２ｍｏｌ／Ｌ含有する硝酸銀水溶液を３．２Ｌ準備し、前記硝酸銀水溶液に濃度２８質量％のアンモニア水溶液を１３７．７ｇ（銀に対して２．７モル当量相当）加えて銀アンミン錯体水溶液を得た。また、７０質量％炭酸ヒドラジン水溶液１４．６ｇ（大塚化学株式会社製、銀量に対して１．８モル当量相当）を純水１３１．４ｇで希釈して還元剤を得た。この銀アンミン錯体水溶液の液温を３０．０℃に維持し、分散剤としてステアリン酸系エマルジョン溶液を０．５９ｇ（ステアリン酸換算で銀に対して０．２質量％）を加えた後に、十分に撹拌している銀アンミン錯体溶液に、上記還元剤を混合して、銀粉を含むスラリーを得た。混合の開始から１．２秒後に、溶液の変色が開始し還元析出反応が起きたことが分かった。
更に得られた銀粉を含むスラリーに対して、分散剤としてエタノールにオレイン酸を５．０質量％になるように溶かした溶液を３．６ｇ加え、十分に撹拌した後、熟成させた。オレイン酸の添加量は、銀粉の質量に対して０．４質量％である。前記熟成されたスラリーを濾過、水洗した後、真空乾燥機を用いて７３℃で１０時間乾燥させた。その後解砕して実施例２の球状銀粉を得た。
(Example 2)
Prepare 3.2 L of a silver nitrate aqueous solution containing 0.12 mol / L as silver ions, and add 137.7 g (equivalent to 2.7 mol equivalents to silver) of an ammonia aqueous solution having a concentration of 28% by mass to the silver nitrate aqueous solution to make silver ammine. An aqueous complex solution was obtained. Further, 14.6 g of a 70 mass% hydrazine carbonate aqueous solution (manufactured by Otsuka Chemical Co., Ltd., equivalent to 1.8 molar equivalents with respect to the amount of silver) was diluted with 131.4 g of pure water to obtain a reducing agent. Sufficiently after maintaining the liquid temperature of this silver ammine complex aqueous solution at 30.0 ° C. and adding 0.59 g (0.2% by mass with respect to silver in terms of stearic acid) of a stearic acid-based emulsion solution as a dispersant. The above-mentioned reducing agent was mixed with the silver ammine complex solution stirred in the above to obtain a slurry containing silver powder. It was found that 1.2 seconds after the start of mixing, discoloration of the solution started and a reduction precipitation reaction occurred.
Further, to the obtained slurry containing silver powder, 3.6 g of a solution prepared by dissolving oleic acid in ethanol in an amount of 5.0% by mass as a dispersant was added, and the mixture was sufficiently stirred and then aged. The amount of oleic acid added is 0.4% by mass with respect to the mass of silver powder. The aged slurry was filtered, washed with water, and then dried at 73 ° C. for 10 hours using a vacuum dryer. Then, it was crushed to obtain spherical silver powder of Example 2.
得られた実施例２の球状銀粉を、走査型電子顕微鏡（ＳＥＭ）を用いて倍率１００００倍で撮影した。撮影した画像を図３に示す。また、得られた実施例２のＳＥＭ画像について、実施例１と同様にしてＭａｃ−Ｖｉｅｗ解析を行った。測定結果を粒度分布としてグラフ化したものを図４に示す。その結果、累積５０％粒子径（Ｄ５０）は０．５０μｍ、粒度分布の標準偏差は０．０６９μｍであり、変動係数は０．１３８であった。 The obtained spherical silver powder of Example 2 was photographed with a scanning electron microscope (SEM) at a magnification of 10000 times. The captured image is shown in FIG. Further, the obtained SEM image of Example 2 was subjected to Mac-View analysis in the same manner as in Example 1. FIG. 4 shows a graph of the measurement results as a particle size distribution. As a result, the cumulative 50% particle size (D50) was 0.50 μm, the standard deviation of the particle size distribution was 0.069 μm, and the coefficient of variation was 0.138.
（比較例１）
銀イオンとして０．１２ｍｏｌ／Ｌ含有する硝酸銀水溶液を３．２Ｌ準備し、前記硝酸銀水溶液に濃度２８質量％のアンモニア水溶液を１３７．７ｇ（銀に対して２．７モル当量相当）加えて銀アンミン錯体水溶液を得た。また、８０質量％ヒドラジン水溶液１１．８ｇ（銀量に対して１．８モル当量相当）を純水１２３．３ｇで希釈して還元剤を得た。この銀アンミン錯体水溶液の液温を３０．０℃に維持し、十分に撹拌している銀アンミン錯体溶液に上記還元剤を混合して、銀粉を含むスラリーを得た。混合を開始してすぐ（０．３秒後）に、溶液が変色し還元析出反応が起きたことが分かった。
更に得られた銀粉を含むスラリーに対して、分散剤としてエタノールにオレイン酸を５．０質量％になるように溶かした溶液を３．６ｇ加え、十分に撹拌した後、熟成させた。オレイン酸の添加量は、銀粉の質量に対して０．４質量％である。前記熟成されたスラリーを濾過、水洗した後、真空乾燥機を用いて７３℃で１０時間乾燥させた。その後解砕して比較例１の球状銀粉を得た。
(Comparative Example 1)
Prepare 3.2 L of a silver nitrate aqueous solution containing 0.12 mol / L as silver ions, and add 137.7 g (equivalent to 2.7 mol equivalents to silver) of an ammonia aqueous solution having a concentration of 28% by mass to the silver nitrate aqueous solution to make silver ammine. An aqueous complex solution was obtained. Further, 11.8 g of an 80 mass% hydrazine aqueous solution (corresponding to 1.8 mol equivalents with respect to the amount of silver) was diluted with 123.3 g of pure water to obtain a reducing agent. The liquid temperature of the silver ammine complex aqueous solution was maintained at 30.0 ° C., and the reducing agent was mixed with the silver ammine complex solution that had been sufficiently stirred to obtain a slurry containing silver powder. Immediately after the start of mixing (0.3 seconds later), it was found that the solution was discolored and a reduction-precipitation reaction occurred.
Further, to the obtained slurry containing silver powder, 3.6 g of a solution prepared by dissolving oleic acid in ethanol in an amount of 5.0% by mass as a dispersant was added, and the mixture was sufficiently stirred and then aged. The amount of oleic acid added is 0.4% by mass with respect to the mass of silver powder. The aged slurry was filtered, washed with water, and then dried at 73 ° C. for 10 hours using a vacuum dryer. Then, it was crushed to obtain a spherical silver powder of Comparative Example 1.
得られた比較例１の球状銀粉を、走査型電子顕微鏡（ＳＥＭ）を用いて倍率１００００倍で撮影した。撮影した画像を図５に示す。また、得られた比較例１のＳＥＭ画像について、実施例１と同様にしてＭａｃ−Ｖｉｅｗ解析を行った。測定結果を粒度分布としてグラフ化したものを図６に示す。その結果、累積５０％粒子径（Ｄ５０）は０．４０μｍ、粒度分布の標準偏差は０．０９６μｍであり、変動係数は０．２３８であった。 The obtained spherical silver powder of Comparative Example 1 was photographed with a scanning electron microscope (SEM) at a magnification of 10000 times. The captured image is shown in FIG. Further, the obtained SEM image of Comparative Example 1 was subjected to Mac-View analysis in the same manner as in Example 1. FIG. 6 shows a graph of the measurement results as a particle size distribution. As a result, the cumulative 50% particle size (D50) was 0.40 μm, the standard deviation of the particle size distribution was 0.096 μm, and the coefficient of variation was 0.238.
これらの実施例および比較例で得られた銀粉の粒度特性を表１に示す。比較例１に対して、実施例１の一次粒子径は小さく、実施例２の一次粒子径は大きいことが分かる。しかしながら、どちらの実施例においても変動係数は比較例１よりも小さい。したがって、還元剤として炭酸ヒドラジンを用いた場合には、その粒径の大小に関わらず一次粒子径が揃うといえる。 Table 1 shows the particle size characteristics of the silver powder obtained in these Examples and Comparative Examples. It can be seen that the primary particle diameter of Example 1 is smaller and the primary particle diameter of Example 2 is larger than that of Comparative Example 1. However, in both examples, the coefficient of variation is smaller than in Comparative Example 1. Therefore, when hydrazine carbonate is used as the reducing agent, it can be said that the primary particle diameters are the same regardless of the size of the particle size.
そして、本発明により、従来の製造方法に対して、高価な試薬や複雑な工程を用いることなく、一次粒子径のばらつきを小さくできたことが分かった。また、排水処理についても、従来のヒドラジン水溶液を用いた場合と同様に行うことができることを確認した。 Then, it was found that the present invention made it possible to reduce the variation in the primary particle size without using expensive reagents and complicated steps as compared with the conventional production method. It was also confirmed that wastewater treatment can be performed in the same manner as when a conventional hydrazine aqueous solution is used.
さらに、これらの実施例および比較例より、炭酸ヒドラジンを用いて作成された球状銀粉は、生産コストを大きく増加させることなく、従来の球状銀粉よりも一次粒子径で見た粒度分布幅が狭くなることが分かった。つまり一次粒子径のばらつきが小さい粒子を作製することが可能となった。 Furthermore, from these Examples and Comparative Examples, the spherical silver powder produced using hydrazine carbonate has a narrower particle size distribution width in terms of primary particle size than the conventional spherical silver powder without significantly increasing the production cost. It turned out. That is, it has become possible to produce particles having a small variation in the primary particle diameter.
以上より、本発明により作成された球状銀粉は一次粒子径が揃うということが分かった。したがって、目的とする粉体特性の達成が容易に可能で、導体パターンの高密度化、ファインライン化などに対応可能なペーストの作成も可能となることが期待される。 From the above, it was found that the spherical silver powder produced by the present invention has the same primary particle size. Therefore, it is expected that it is possible to easily achieve the desired powder characteristics, and it is also possible to produce a paste that can be used for increasing the density of conductor patterns and making fine lines.
Claims (5)
該銀アンミン錯体は、硝酸銀、銀錯体及び銀中間体の少なくともいずれかを含有する水溶液にアンモニア水又はアンモニウム塩を添加することにより調液される、請求項１または２に記載の球状銀粉の製造方法。 The aqueous reaction system containing the silver ion is a silver ammine complex.
The production of the spherical silver powder according to claim 1 or 2, wherein the silver ammine complex is prepared by adding aqueous ammonia or an ammonium salt to an aqueous solution containing at least one of silver nitrate, a silver complex and a silver intermediate. Method.
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| EP19837339.1A EP3825040A4 (en) | 2018-07-17 | 2019-07-17 | Method for producing spherical silver powder |
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